Owing to their widespread properties, nitridophosphates are of high interest in current research. Explorative high-pressure high-temperature investigations yielded various compounds with stoichiometry MP 2 N 4 (M = Be, Ca, Sr, Ba, Mn, Cd), which are discussed as ultra-hard or luminescent materials, when doped with Eu 2 + . Herein, we report the first germanium nitridophosphate, GeP 2 N 4 , synthesized from Ge 3 N 4 and P 3 N 5 at 6 GPa and 800 °C. The structure was determined by single-crystal X-ray diffraction and further characterized by energy-dispersive X-ray spectroscopy, density functional theory calculations, IR and NMR spectroscopy. The highly condensed network of PN 4 -tetrahedra shows a strong structural divergence to other MP 2 N 4 compounds, which is attributed to the stereochemical influence of the lone pair of Ge 2 + . Thus, the formal exchange of alkaline earth cations with Ge 2 + may open access to various compounds with literature-known stoichiometry, however, new structures and properties.Nitridophosphates are an extremely diverse class of materials attracting high interest in current research. Their wide range of applications and intriguing materials properties emerge from the structural versatility, which competes with the earth's predominant class of materials, the (oxo)silicates. [1] Due to the isoelectronic combination of elements Si/O and P/N, both form similar structural motifs, most commonly SiO 4 -and PN 4 -tetrahedra. In the majority of cases, these building blocks are arranged in three-dimensional anionic networks or two-dimensional layers. The

Recent advances in methods to access nitride systems by a high-pressure high-temperature approach have made possible the one-step synthesis of mixed ternary non-metal nitrides. As a prerequisite to use in...

Layered silicates are a very versatile class of materials with high importance to humanity. The new nitridophosphates MP6N11 (M=Al, In), synthesized from MCl3, P3N5 and NH4N3 in a high‐pressure high‐temperature reaction at 1100 °C and 8 GPa, show a mica‐like layer setup and feature rare nitrogen coordination motifs. The crystal structure of AlP6N11 was elucidated from synchrotron single‐crystal diffraction data (space group Cm (no. 8), a=4.9354(10), b=8.1608(16), c=9.0401(18) Å, β=98.63(3)°), enabling Rietveld refinement of isotypic InP6N11. It is built up from layers of PN4 tetrahedra, PN5 trigonal bipyramids and MN6 octahedra. PN5 trigonal bipyramids have been reported only once and MN6 octahedra are sparsely found in the literature. AlP6N11 was further characterized by energy‐dispersive X‐ray (EDX), IR and NMR spectroscopy. Despite the vast amount of known layered silicates, there is no isostructural compound to MP6N11 as yet.

We report the first characterization of a newly synthesized germanium nitridophosphate, GeP2N4. GeP2N4 is structurally distinct from all other known MP2N4 systems (M = Be, Ca, Sr, Ba, Mn, Cd)...

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